Process for producing chlorine and recovering substantially pure hydrogen chloride from the hot reaction product



Feb. 8, 1966 ALKEMADE 3,233,978

PROCESS FOR PRODUCING CHLORINE AND RECOVERING SUBSTANTIALLY PURE HYDROGEN CHLORIDE FROM THE HOT REACTION PRODUCT Filed Dec. 2, 1963 SORUBBINO ZONE OHLORINE WATER AND INPURITIES ZONE OISTILLATION OHLORINE SEPARATING ZONE WATER OUENCHING ZONE REACTION ZONE INVENTOR:

ALPHONSUS M. ALKE MADE HIS AGENT United States Patent 3,233,978 PROCESS FOR PRODUCING CHLORINE AND RECOVERING SUBSTANTIALLY PURE HY- DROGEN CHLORIDE FROM THE HOT RE- ACTION PRODUCT Alphonsus M. Alkemade, The Hague, Netherlands, as-

signor to Shell Oil Company, New York, N.Y., a corporation of Delaware Filed Dec. 2, 1963, Ser. No. 327,195 Claims priority, application Netherlands, Dec. 5, 1962,

Claims. (Cl. 23-219) This invention relates to an improvement in the recovery of hydrogen chloride free of any substantial amount of Water from gaseous reaction products obtained at elevated temperatures containing hydrogen chloride in admixture with water vapor and normally gaseous materials comprising chlorine. The invention relates more particularly to the recovery of substantially anhydrous hydrogen chloride, in a high stateof purity, from the hot reaction mixtures comprising water and chlorine produced by reaction of hydrogen chloride with oxygen in the presence of a solid catalyst at elevated temperatures.

The process of the invention is applied broadly to the recoveryof hydrogen chloride free of any substantial amount of water, and in a high state of purity from gaseous mixtures containing hydrogen chloride in admixture with normally gaseous materials including chlorine and water vapor obtained at elevated temperatures.

The invention is applied with particular advantage to the recovery of hydrogen chloride, free of any substantial amount of water, from the impure, hot, gaseous reaction mixtures obtained in the production of chlorine by the reaction of hydrogen chloride with oxygen, or an oxygen-containing gas, in the presence of a suitable solid catalyst, for example, a metal compound-containing catalyst such as a copper chloride-containing catalyst. This reaction is known to proceed in the general temperature range of, for example, from about 300 to about 600 C. resulting in a gaseous reactor effiuence the temperature of which is in this range. However, until recently the execution of this reaction at temperatures of approximately 400 C. and lower was often only a theoretical possibility. The catalysts used generally did not enable the reaction to proceed at these temperatures at a rate commensurate with practical scale operation. At the high temperatures, of necessity employed in these processes, equilibrium for the reaction is attained only at relatively low conversions and conversions of only 30 to 40% were often not surpassed. The need to rely upon such relatively inefiicient methods of operation has been obviated by the method disclosed and claimed in copending US. application Serial No. 83,134, filed January 17, 1961, for the oxidative catalytic conversion of hydrogen chloride to chlorine with the aid of a catalyst enabling the execution of the reaction to proceed not only at substantially lower temperatures, but with attainment in practical scale operation of conversions corresponding substantially to the theoretical equilibrium value for the reaction. As is known, the theoretical equilibrium values become progressively more favorable with decreasing temperatures. Conversions of the order of about 75% are readily achieved in the process described and claimed in said copending application. Since the reaction involved in the oxidative conversion of hydrogen chloride to chlorine is equilibrium reaction the hot reactor efiluence will always comprise, even at the high conversion levels, some unconverted hydrogen chloride in addition to chlorine and Water vapor. If the reactants charged are not pure, additional components are present in the reaction mixture. When using air as the oxygen source the hot reactor etlluence will additionally comprise nitrogen.

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In separating chlorine from such hot gas mixtures obtained by the catalytic oxidation of hydrogen chloride, the first step generally is to reduce its temperature, for example, to about 40 C150 C. This may be done by quenching with water and/or hydrochloric acid. After quenching the gas mixture may be further worked up by various procedures; for instance by washing with water and/or dilute hydrochloric acid (in which case a large portion of any water vapor present will also condense), or by cooling the gas mixture to such an extent that at least a part of the Water vapor present therein condenses and the hydrogen chloride gas is dissolved therein. The residual chlorine-containing gas can then be dried. Finally chlorine may be separated [from the gas mixture, for example, by liquefaction at elevated pressure, solvent extraction using a suitable solvent, such as carbon tetrachloride. Recourse to such method of product resolution generally results in the obtaining of the hydrogen chloride component as aqueous hydrochloric acid. It is, however, often desirable, and at times essential to practical operation, that the hydrogen chloride be returned to the reaction for further conversion to the desired chlorine. Efiicient operation precludes the introduction of any substantial amounts of aqueous hydrogen chloride (hydrochloric acid) into the reaction zone. The recycling of the hydrogen chloride can "therefore generally not be resorted to in operations wherein this component is recovered as aqueous hydrogen chloride (hydrochloric acid) without adversely effecting the efficiency of the process. To convert such aqueous hydrogen chloride product in a separate operation to substantially anhydrous hydrogen chloride suitable for recycling not only present difficult technical problems but increases inordinately the cost of the overall operation. A process enabling the efficient recovery of hydrogen chloride in substantially anhydrous form suitable for recycling, and chlorine, with a minimum of operative steps, from the hot reaction mixtures obtained in the catalytic oxidative conversion of hydrogen chloride to chlorine is therefore of exceeding importance to the industry.

It is therefore an object of the present invention to provide an improved process enabling the more efficient recovery of hydrogen chloride free of any substantial amount of water from hot gaseous reaction mixtures comprising hydrogen chloride in admixture with water vapor and normally gaseous materials comprising chlorine. Another object of the invention is the provision of an improved process enabling the more efiicient recovery of substantially anhydrous hydrogen'chloride from the hot gaseous mixtures containing hydrogen chloride in admixture with chlorine, water vapor and fixed gas produced by catalytic oxidative conversion of hydrogen chloride.

Still another object of the present invention is the provision of an improved process enabling the more efiicient production of chlorine by catalytic oxidative conversion of hydrogen chloride providing for the inherent recovery and recycling to the reaction zone of unconverted hydrogen chloride in substantially anhydrous form. Other objects and advantages of the present invention will become apparent from the following detailed description thereof made with reference to theattached drawing wherein the single figure represents a diagrammatic elevational view of one form of apparatus suitable for carrying out the process of the invention.

The process of the invention provides a method enabling not only substantially complete recovery of both the chlorine and hydrogen chloride components of the hot reaction mixture charged, but provides for inherent separation between hydrogen chloride and Water with a minimum operative steps, thereby making possible the efficient recovery of the hydrogen chloride in substantially anhydrous form.

Within the system, subjecting the resulting quenched reaction mixture to countercurrent direct contact with liquid solvent for hydrogen chloride gas in said extraetion zone, thereby separating a vapor overhead rafiinate fraction comprising Water vapor and chlorine from a liquid bottom extract fraction comprising enriched hydrochloric acid in the lower part of said extraction zone, introducing liquid dilute hydrochloric acid emanating from within the system into said extraction zone at an intermediate point thereof as said solvent for hydrogen chloride gas, introducing liquid Water assupplementary solvent for hydrogen chloride gas into said extraction zone at a point near the withdrawal of said vapor overhead rafiinate fraction therefrom, passing a part of said liquid bottom extract fraction from said extraction-zone into said quenching zone to be used therein as said hydrochloric acid emanating fromwithin the system, passing the remainder of said bottom extract fraction from said extraction zone into a distillation zone, distilling hydrogen chloride free of any substantial amount of water from liquid still bottoms consisting essentially of dilute hydrochloric acid approximating the hydrogen chloride water azeotrope in said distillation zone, passing said liquidstill bottoms from said distillation zone into said extraction 1 zone at said intermediate point thereof to be used therein as said dilute hydrochloric acid emanating from within the system, separating chlorine from said vapor overhead fraction separated in said extraction zone, and controlling the temperature at whichsaid dilute hydrochloric acid and water solvent streams are introduced into said extrac tion zone to maintain the sum total of Water Withdrawn overhead from said extraction zone and in the uncondensed overhead eliminatedfrom said distillation zone substantially equal to the total amount of water introduced into said quenching and extraction zones from outside the recovery system.

When the recovery process of the'invention is integrated with the reaction system producing the hot gaseous mixture processed, for example, by the catalytic oxidative conversion of hydrogen chloride to chlorine, the overhead from the distillation zone of the recovery system, consisting essentially of hydrogen chloride free of any substantial amount of water, is recycled directly to the reaction zone. The integrated recycle process of the invention thus enables the substantially complete conversion of the hydrogen chloride charge to the catalytic oxida'- tive conversion to chlorine with substantially improved efliciency.

Referring to the figure in the attached drawing: Hydrogen chloride, emanatingfrom an outside; source through line 10, provided with valve 11, is forced into line '12 wherein it mixes withhydrogen chloride recycled from within the system as described below. An oxygen-con: taining gas, for example, air is introduced into line 12 from an outside source through line 13, provided with valve 14. The resulting admixture of air and-hydrogen chloride passes from line 12 .into a reaction zone, com-- prising, for example, a suitable reactor 15 wherein the mixture is subjected to oxidative conversion conditions to effect the oxidative conversion of hydrogen chloride to chlorine. Suitable oxidative reaction conditions comprise'those described and. claimed in copending US. application Serial No. 83,134 above referred to including, for example, the presence of a catalyst consisting essentially of a mixture of copper chloride-potassium chloridedidymium chloride and a suitable solid. support, such as finelydivided silica, and a temperature in the range 4; of about 300400 C. Although the use of such reaction conditions are preferred as the source of the hydrogen chloride-containing gaseous mixture treated in accordance with the invention, it is to be understood that the invention is not necessarily limited with respect to the specific reaction conditions employed in .the. production of the.

gaseous mixture subjected to the process of the invention, and any conditions producing the; suitable gaseous hydrogen chloride containing. charge may suitably be employed in reactor 15.

Reactor .efliuence, for example,'at-, a temperature of from about 250 to about 400 C. comprising unconverted hydrogen chloride in admixture with watervapor, chlorine, fixed gases including oxygen, nitrogen, oxides of carbon, as well as any organic impurities, is passed from reactor 5,.through line 17 into a suitable quenching zone.-' The quenching zone may comprise a zone of enlarged-crosssectionalarea such as, forexample, achamber 20. A

suitable quenching zone may comprise instead, or in addition, an enlarged pipe, coil or the like, suitable for;

assuringintimate contactof the quenching medium with the hot reactor eflluence. providedrwith suitable bafiles, venturi injectors, and the like.

A line -18,- provided with valve 19, discharging into line 17, is provided for the introduction of suitable hot hydrogen chloride-containing gas, of the type described herein as suitable for treatment in accordance with theinvention, into the system from any suitable outside source. Such gaseous mixture introduced throughvalved line 18,. may constitute a part or all of the gaseous mixture charged through line 17 into chamber 20.1

Within chamber 20v .the hot gasmixture is quenched" with with a suitable, quenching. medium such as, forexample; hydrochloric acid emanating from within the. system through line 22* provided with valve 23. There is a large. degree of freedom in the temperature towhich the hot gas mixture passing through line. 17 is cooled in quenchingchamber 20. Quenching is controlled by the quantity of quenching liquid supplied through line 22. coolingis carried out in chamber 20 to below the dewpoint of. the resultant gas mixture, a mixture of gas and,

liquid will result. In, generaLquenchingthe hot gases to a temperature. in the range of from about 40 to about, a

150 C; is-satisfactory; From chamber 20, the quenchedmixture is passed through line 21 into a suitable chlorine separating zone. Thesuitable chlorineseparating zone may comprise, for example, an extraction column 25..

solvent. mixture is brought into directcountercurrent contact with a stream; of liquid solvent comprising an admixture of i (a) dilute hydrochloric acid, for example, having the approximate composition of thehydrogen chloride-water.

azeotrope emanating from within the system, and intro-. duced into columnZS/at an intermediate point thereof, by means of line 30 and (b) a rich liquid absorbate, con-' sisting, essentially of dilute hydrochloric acid,.flowing.

down from the upper part of thecolumn 25. 1 A substantial part of the hydrogen chloride content of the quenched mixture will be absorbed by the solvent stream in the lower part of column 25 -withrthe separation of a rich liquid .absorbate consisting, for example, of more concenof. column 25 .by means of-line 31 provided with heating: means, for example,.heater 33 and, a valve 32. The water 1 introduced through line,31 from an outside source is preheated in heater 32 before entering the top of column 25.

The suitable preheating temperature may varyras defined These may furthermore be,

below; In a. preferred method of operation the water entering through line 31 is preheated to the temperature prevailing in the upper part of column 25. In the upper part of column 25 the liquid water scrubs out substantially all of the remaining hydrogen chloride to form a dilute hydrochloric acid which passes downwardly into the lower part of column 25 as supplementary solvent. The gaseous mixture leaving the upper part of column 25 comprising water vapor, chlorine and fixed gases comprising nitrogen,.oxides of carbon, now free of any substantial amount of hydrogen chloride is passed through line 70 provided with valve 71 to suitable chlorine separating means and optionally purifying means. The liquid absorbate bottom fraction consisting essentially of the more concentrated or enriched hydrochloric acid is taken from the bottom of column 25 and forced through line 40, provided with valve 42, by means of pump 41, into a suitable distillation zone, comprising, for example, distillation column 45 and condenser 49.

A part of the stream of hydrochloric acid flowing through line 40 is diverted through line 22, provided with valve 23, into quench chamber 20 to be used therein as the quenching medium emanating from in the system referred to above.

, Within distillation column 45 hydrogen chloride is distilled from the relatively concentrated hydrochloric acid charged thereto through line 40 leaving as liquid distillationbottoms in still 45 a dilute hydrochloric acid having the approximate composition of the hydrogen chloridewater azeotrope. ,A closed heating coil 46 in the lower part of still 45, and an indirect heat exchanger 43 positioned in line 40, provide the necessary heat for the distillation.

q Distillation bottoms are withdrawn from the bottom of distillation column, 45 and passed through line 60, provided with valve 59, through exchanger 43, and through cooler 61, into line 30 discharging into an intermediate part of column 25 to provide the dilute hydrochloric acjdemanating thereto from within the system and used therein as the solvent referred to above. A by-pass line 62 leading from line 59 into line 30 is provided to enable the by-passing of cooler 61. A three-way control valve 63 is PIOVldCdLtO control the relative flow from lines 60 and 62 into line 30.

y The overhead from distillation column consisting of hydrogen chloride and water vapor is passed therefrom through line 12 into condenser 49 wherein the stream is cooled to condense substantially all of the water content thereof. The water so condensed is returned via line 50 provided with valve 51 to the upper part of still 45 as reflux. The hydrogen chloride, free of any substantial amount of water, is forced through line 12 by means of pump 52 to the reactor 15. The hydrogen chloride gases leaving condenser 49' through line 12 may stillcontain a small quantity of water vapor. This gas may be safely returned to the oxidation reactor, because the quantity of water vapor is so slight that the oxidation reaction is hardly-influenced by it. If desired, however, the quantity of water vapor in the-gas leaving condenser 49 may be reduced by cooling to a lower temperature in the condenser 33. Y

The conditions within still 45 may vary widely but in general distillation under elevated pressure is advantageous, because at higher pressures the azeotropic composition of hydrochloric acid shifts to smaller HCl concentrations. Moreover, in this case the hydrogen chloride gas becomes available under super-atmospheric pressure which is desirable when his intended to return this gas to the oxidation reactor.

It has been stated above the hydrochloric acid of substantially azeotropic composition collects in the bottom part of the still 45 and is withdrawn therefrom through the line 60. The HCl concentration of the acid is generally a little higher than the azeotropic concentration. In theory it would benecessary to operate in a distillation column with an infinite number of theoretical trays in order. to obtain acid of the exact azeotropic composition. In practice it would be possible to approximate to the azeotropic composition as closely as desired by using a column with a sufficient number of theoretical trays. However, practice also sets limits to the cost and the effort which may reasonably be devoted to the distillat1o n. Thls means that in practice the production of an acidthe composition of which slightly deviates from the azeotropic composition has to be accepted. The expressions hydrochloric acid of azeotropic composition and hydrochloric acid azeotropic as usedin the specification and the claims, should be understood in this sense. Thus, the distillation bottoms in still 45 may consist of hydrochloric acid of about 18% by weight concentration.

It will be apparent that column 25 may be viewed as comprising two consecutive extraction zones, lower section 27 and upper section 26, arranged in series flow and separated by bubble plates 35 and 36. The rich liquid aqueous absorbate leaving section 26 at the bottom thereof admixes with the dilute acid solvent entering in line 30 and the resulting liquid admixture continues into and downward through the lower section 27. Comprised within the scope of the invention is the use of two separate extraction columns arranged in series flow to replace sections 26 and 27 of column 25.

The extraction sections 26 and 27 of column 25 may optionally be packed with suitable packing material such as, for example, Raschig-rings or the like. Column 25 may be constructed of material which is resistant to' the materials coming into contact therewith. A steel column lined with acid-resisting ceramic material, with an intermediate rubber layer is satisfactory.

Essential to the attainment of the objects of the invention is the maintaining of conditions such'that the total quantity of water taken overhead from column 25 through line 70 and condenser 49 through line 12 is equal to the total amount of water introduced into chamber 20 through line 17 and into the upper part of column 25 through line 31; 'As' indicated above the quantity of water leaving condenser 49 with the uncondensed stream through line 12 will generally be small. The limiting conditions are attained in the system represented in the figure of the attached drawing. Thus, equivalence of the total amount of water introduced into the system through lines 17 and 31, to the total amount leaving column 25 throughline 70 and condense'r49 through line 12 means that the total quantity of water present in the system remains substantially constant; inequality of these quantities results in an increase or decrease in the total quantity of water present in the system. There are two important liquid levels in the system, viz. in column 25 AB and CD in still 45. Any substantial variation in the total quantity of water present in the system is reflected by a rise or drop in these liquid levels. Liquid level CD is, however, kept constant by means of a liquid level controller 90, operating a valve in the line 60.

If level CD is kept constant, any increase or decrease in the total quantity of water in the system is reflected as a rise or a drop in level AB. Level AB is controlled by a level controller 91, which operates a temperature controller connected to line 30, which in turn operates the control valve 63. A rise in level AB means that the total quantity of water in the system increases so that too little water vapor is drawn oif through line 70. Control valve 63 will then so adjust by the control equipment that a larger portion of hydrochloric acid supplied through line 60 passes through line 62 and a smaller portion through cooler 61, so that the-hydrochloric acid introduced into column 25 through line 30is brought to a higher temperature. Since in this way more heat is supplied to column 25, the temperature at the top of the column rises and consequently the saturated water vapor pressure above the liquid rises, as a result of which a drop in level AB is counteracted by control valve 63 in such a way that ofthe hydrochloric acid supplied through the line 60 a smaller'portion passes through line 62 and a larger portion through cooler 61.

This method of controlling thesystem ensures that the quantity and the temperature of the water supplied through line 31 are kept constant. Fluctuations in: the total supply to column 25 are primarily caused by fluctuations in the composition of the gas mixture supplied through line 17. By means of the control method described, however, the system adapts itself to these fluctuations.

The described control of the temperature of the hydrochloric acid introduced into column 25 through line 30 is suflicient to operate the system. The system auto-. matically finds a state of equilibrium and a new state of equilibrium is automatically reached when the circumstances change. The temperature in column 25 :is affected by three important heat effects. The first is the liberation of heat in the absorption in water of hydrogen chloride gas supplied through the line 17. The second is the liberation of heat owing to the condensation of water and the absorption of hydrogen chloride gas, which have been introduced as liquid hydrochloric acid into quenching chamber through line 22, have been evap-. orated therein, and are'now introduced in vapor form into column through line 21. The third is the consumption of heat for the evaporation of water supplied through line 31, which water again escapes as vapor from column 25' through line 70. If for one reason or another, the oxidation reaction is proceeding less satisfactorily, then the gas mixture supplied through line 17 will contain an increased amount of hydrogen chloride 1 and less water. More HQ must therefore be absorbed in the column 25,, so that more heat-is liberated and the temperature tends to rise. When the temperature .at the top of column 25 is raised, the gas mixture passing through'line 70 will contain more water vapor. The quantity, of water in the system will decrease and level AB will drop. In the manner described above, the temperature of the hydrochloric acid introduced through line will be reduced by means of the control equipment. As a result the temperature in column 25 tends to drop, which counteracts the above-mentioned tendency torise.- The result is that a state of equilibrium is quickly attained again.

There is a large measure of freedom in the choice, of the temperature and the quantity of the Water supplied through line 31 and in the coolingtemperature in cooler 61. In a preferred method of control these magnitudes are chosen as follows: The temperature of the water sup-. plied through line 31 is preferably so chosen that it is approximately equal to the temperature in the top of column 25 in normal operation. The quantity of this water is preferably so chosen'that owing to the evaporation heat of this water the column operates approximately adiabatically. In this case it is not necessary to use the temperature of the hydrochloric acid supplied through the line 30 in order to keep column 25 in heat balance, so that this acid may enter the column at approximately the same temperature as the temperature prevailing in situ in the column. Since this acid is supplied through line 60 and control of the temperature of the acid in the line 30 is easiest when, in normal operation, approximately the same quantity of acid flows through line 62 and cooler 61 the cooling temperature in cooler 61 is set at a fixed value, for example, about 80 C. After the teme perature and the quantity of the. ,water supplied through line 31 and the cooling temperature in cooler 61 have compositionof the gas mixture supplied through the line 17, as described above.

In practice this is readily realized because,.with agiveri composition of the gastmixture' supplied through the line 17, the heat-effects: inthe column 25: maybe calculated;

On this basis, the cooling temperature in cooler '61 and the temperature in heater; 33 are .set and-approximately the correct water stream through line 3L is thenchosen.

If it appears that with the chosen water'flo'wrate through line 31, very unequal streams of hydrochloric acid through.

line. 62- and cooler 61- are necessary, they flow rate through the line 31 is adjusted, so that the column operates with. approximately equal streams of hydrochloric acid through ing. This maybe carried out quite readily under conditions elfectin'g simultaneous removal of organic impurities such as, for example,:C Cl To this effect line 70 is discharged into a scrubbing zone, comprising, for example, a tower 72,?wherein thegaseousstream passes upward countercurrent- :to a spraywof water introduced through lines 73,75, 76 and.77." This water is cooled to a. low temperature, for example, "below about 15 C.

with the aid of cooler 74 and other means not shown in;

the drawing; Asa result of such cooling both water vapor and C Cl condense from the gaseous stream. A liquid phase, (levelGH) collects in the lower part of tower 72. This liquid consisting essentially of water; and sus+ pended crystallized C CIG, if the latter impurity was 'prescut, is drawn from tower 72 through valved line 80.

The scrubbed gas consisting essentially of chlorine and nitrogen is taken :overhead from tower 72 through valved line 79.

Example Thennmbers in parenthesis given in the following example -refer to the similarly numbered parts of the apparatus shown in the attacheddrawing and referred to in the above detailed description of the invention.

A'gaseous streamof 5,241 kg./hr., obtained'by the catalytic .oxidative conversionzof hydrogen'chloride withair ina reactor (15) at 365 C. under the conditions described in- US. application Serial No. 83,134 filed Jane uary 17, 1961, is found to have the following compositions in parts by weight:

HCI 667 H20 521 822C153,

2 r- Cl 1,900

The gaseous mixture is cooled from.365 to C. by quenching. with 600 kg./ hr. of hydrochloric acid of a concentration of 23.5% by weight, that is 141 kgJhr. HCl +459 kg./Vhr. H O, of 95 C., in a quenching chamber 20; the hydrochloric acid so added as quench emanates from within thesystern and is totally vaporized. The resulting gaseous mixture .now contains 808 kg./hr. of HCl and 980 kg./ hr. of H O'; its composition is unaltered as regards the other-components so thatthe total gasstream is now 5,841 kg./hr.;vits'temperature is 95 C. and the pressure 1.5 atm. abs. This gas mixture is introduced into the lower part of an extraction column :25 wherein it is contactedin succession first with a liquid stream of dilute hydrochloric acid 27 emanating from within the system and with a stream of preheated water 26. 1,075 kg./hr. of water preheated 33 to 90 C. are introduced into the top 31 of the extraction column 25. Into an intermediate part 30 of the extraction column 25 there are introduced 9,255 kg./hr. of dilute hydrochloric acid, at 97 C., having a concentration of 18% by Weight. A liquid fraction consisting of hydrochloric acid having a concentration of 23.5% by weight, and which is at a temperature of 95 C., accumulates as bottom liquid (AB) in the extraction column 25.

The liquid bottoms are drawn from the extraction column 25 at the rate of 10,527 kg/hr. 40. Of the liquid bottoms so withdrawn from the extraction column 25 600 kg./hr. flow 22 to the quenching chamber 20 to be used therein as the quenching medium referred to above. The remainder of the liquid bottoms 25 9,927 kg./hr. flow 40 through a prehe'ater 43 wherein they are preheated to 135 C., into a still 45. The still 45 is operated at a bottom still temperature of 151 C. with a pressure of 4.0 atm. abs. in the lower part, and 3.9 atm. abs. in the upper part. Hydrogen chloride and water vapor are distilled overhead leaving as still bottoms hydrochloric acid of 18% by weight concentration (CD). The still bottoms are continuously withdrawn 60 at the rate of 9,255 kg./hr. and sent to the intermediate part 30 of the extraction column 25 to be used therein as the dilute acid referred to above. The still bottoms passing to the extraction column are first cooled by indirect exchange 43 with still charge to 110 C. Of the cooled 43 still bottoms a 4,000 kg./hr. portion is further cooled in a cooler 61 to 80 C. and thereafter recombined with the remaining 5,245 kg./hr. still bottoms stream. The recombined 9,255 kg/hr. stream of still bottoms 30 now at a temperature of 97 C. is then introduced into the extraction column 25 at an intermediate part thereof 30 as referred to above.

With a top still 45 temperature of 146 C. there are taken as overhead 1,747 kg./hr. of hydrogen chloride and 1,193 kg./hr. of water vapor. The still overhead is passed into a condenser 49 wherein it is cooled to 40 C., resulting in the condensation of 1,080 kg./hr. of HCl and 1,188 kg./hr. of H as hydrochloric acid which is re turned 50 to the still as reflux. The uncondensed gas consisting of 667 kg./hr. of HCl and 5 kg./hr. of H 0 is withdrawn from the condenser 49 and recycled 12 to the reaction zone.

The gaseous overhead leaves 32 the extraction column 25 at the rate of 5,644 kg./hr., at a temperature of 90.5 C., a pressure of 1.5 atm. abs., and has the following composition in parts by weight:

N 1,952 co 35 C1 1,900 CCL; 9

It is seen that the gaseous stream leaving 70 the extraction column 25 as overhead, combined with the gaseous stream recycled 12 from the still-overhead condenser 49, equals the composition and weight of the gaseous mixture charged 17 to the quenching chamber 20 and as water supplementary solvent to the top 31 of the extraction colum 25. Complete recovery of the hydrogen chloride component of the charge to the recovery system, free of any substantial amount of water, is thus attained.

The chlorine-containing gaseous stream eliminated overhead from the extraction column 25 is passed 70 into a scrubbing tower wherein it is scrubbed with 17,900 kg./hr. of water. The scrubbing water enters the tower 72 through a plurality of distributors at a temperature of from 10 to 15 C. to remove water vapor and impurities including C Cl by condensation. The overhead 79 from the scrubbing tower 72 has the following composition in parts by weight:

Liquid bottoms are continuously withdrawn 80 from the lower part of the scrubber 72 at the rate of 19,470 kg./hr. of water containing 43 kgl/hr. of C Cl and 14 kg./hr. of chlorine and eliminated from the system.

I claim as my invention:

1. The process for the recovery of hydrogen chloride, free of any substantial amount of water, and chlorine from a hot gaseous reaction mixture containing hydrogen chloride in admixture with water vapor and chlorine by the combination of steps consisting essentially of: quenching said hot reaction mixture to a temperature in the range of from about 40 to about C. in a quenching zone with a member of the group consisting of Water and hydrochloric acid, subjecting the resulting quenched reaction mixture to countercurrent direct contact with liquid solvent for hydrogen chloride gas in said extraction zone, thereby separating a vapor overhead rafiinate fraction comprising water vapor and chlorine from a liquid bottom extract fraction comprising enriched hydrochloric acid in the bottom of said extraction zone, introducing liquid dilute hydrochloric acid emanating from within the system into said extraction zone at an intermediate point thereof as said solvent for hydrogen chloride gas, introducing liquid Water as supplementary solvent for hydrogen chloride gas into said extraction zone at a point near the withdrawal of said vapor overhead raffinate fraction therefrom, passing said bottom extract fraction from said extraction zone into a distillation zone, distilling hydrogen chloridefree of any substantial amount of water from liquid still bottoms consisting essentially of dilute hydrochloric acid in said distillation zone, passing said liquid still bottoms from said distillation zone into said extraction zone at said intermediate point thereof to be used therein as said dilute hydrochloric acid emanating from within the system, separating chlorine from said vapor overhead fraction separated in said extraction zone, and controlling the temperature at which said dilute hydrochloric acid and water solvent streams are introduced into said extraction zone to maintain the sum total of water withdrawn overhead from said extraction zone and in the uncondensed overhead eliminated from said distillation zone substantially equal to the total amount of water introduced into said extraction and quenching zones from outside the recovery system.

2. The process for the recovery of hydrogen chloride, free of any substantial amount of water, and chlorine from a hot gaseous reaction mixture containing hydrogen chloride in admixture with water vapor and chlorine by the combination of steps consisting essentially of: quenching said hot reaction mixture in a quenching zone to a temperature in the range of from about 40 to about 150 C. with hydrochloric acid obtained within the system, subjecting the resulting quenched reaction mixture to countercurrent direct contact with liquid solvent for hydrogen chloride gas in said extraction zone, thereby separating a vapor overhead rafiinate fraction comprising water vapor and chlorine from a liquid bottom extract fraction comprising enriched hydrochloric acid in the bottom of said extraction zone, introducing liquid dilute hydrochloric acid emanating from within the system into said extraction zone at an intermediate point thereof as said solvent for hydrogen chloride gas, introducing liquid water as supplementary solvent for hydrogen chloride gas into said extraction zone at a point near the withdrawal of said vapor overhead raflinate fraction therefrom, passing a part of said liquid bottom extract fraction from said extraction zone into said quenching zone to be used therein as said hydrochloric acid emanating from within the system, passing the remainder of said bottom extract fraction from said extraction zone into a distillation zone, distilling hydrogen chloride free of any substantial amount of water from still bottoms consisting essentially of dilute hydrochloric acid approximating the hydrogen chloride-water azeotrope in said distillation zone, passing said liquid still bottoms from said distillation zone into said extraction zone at said intermediate point thereof to be used therein; as said dilute hydrochloric acid emanating from within,

the system, separating chlorine from said vapor overhead fraction separated in said extraction zone, and controlling the temperature at which said dilute hydrochloric acid and water solvent streams are introduced into said extraction zone to maintain the sum total of waterwithdrawn overhead from said extraction zone and in the uncondensed overhead eliminated from said distillation zone substantially equal to the sum total amount'of water introduced into said quenching and extraction zones from outside the recovery system.

3. The process in accordance with claim 2 wherein said Water introduced into said extraction zone as supplementary solvent is preheated before its introduction into said extraction zone.

4. The process in accordance with claim 3 wherein said water introduced into said extraction zone near the point of withdrawal of said overhead vapor raflinate fraction therefrom is heated to a temperature substant-ially equal to that prevailing in the upper part of said extraction zone, and controlling the temperature of the dilute liquid hydrochloric acid introduced into said extractionzone at an intermediate point thereof to maintain the sum total of water withdrawn overhead from said extraction zone and in the uncondensed gaseous overhead from said distillation substantially equal .to the total amount of water entering said quenching and extractiontzones from outside the recovery system.

5. In the process for the substantially complete conversion of hydrogen chloride to chlorine in a process wherein hydrogen chloride is reacted with air in the presence of a catalyst consisting essentially of copper 'halidelin admixture with a lanthanide "halideland potas- 1 'siumhalide at a temperature of from'about 300 to about 600 (3., thereby forming a reaction: mixture comprising o hydrogen chloride in admixture with water vapor and chlorine in a reaction zone, the combination of steps consisting essentially of: quenching said reaction mixture in a quenching zone to a temperature'in the range of from about 40 to about C; with hydrochloric acid obtained within the system, subjecting the resulting quenched reaction mixture to countercurrent direct contact W-i-th liquid solventz-for hydrogen chloride gas in said extraction zone, thereby separating a vapor overhead raflinate fraction comprising water vapor :andlchlorine from a'liquid bottom extract fraction comprising enzone, introducing liquid dilute hydrochloric acid emanatriched hydrochloric acid inethe bottom of said extraction 1 ing from within the system into said extraction zone at an intermediate pointthereof as said solvent-for hydrogen chloride gas,,- introducing liquid water, as supplementary solventzfor hydrogen chloride gas into said extraction zone at a point near the withdrawal of said vapor overhead raifinate fraction therefrom, passing a partof said liquid bottom extract fractionfrorn said extraction zone into said quenching zone to be used therein as said hydrochloric acid emanating .from within the system,

passing the remainder of said bottom extract fraction from said extractionszone into a distillation zone, dis- 1 tilling hydrogen chloride free'of any substantial amount of water from still bottoms consisting essentially of dilute hydrochloric acid approximating the hydrogen chloridewater azeotrope in said distillation zone, .passing said liquid still bottoms from said distillation zone into said extraction zone at said intermediate pointvthereof to be used therein as said dilute hydrochloric acid emanating from within the system,separating chlorine from said and in the uncondensed overhead eliminated from said distillation zone substantially equal to the total amount of water introduced into said quenching zonevand as supplementary solvent into said extraction zone, and recycling uncondensed overhead from said distillation zone to saidreaction zone.

No references cited.

BENJAMIN HENKIN, Primary Examiner. 

5. IN THE PROCESS FOR THE SUBSTANTIALLY COMPLETE CONVERSION OF HYDROGEN CHLORIDE TO CHLORINE IN A PROCESS WHEREIN HYDROGEN CHLORIDE IS REACTED WITH AIR IN THE PRESENCE OF A CATALYST CONSISTING ESSENTIALLY OF COPPER HALIDE IN ADMIXTURE WITH A LANTHANIDE HALIDE AND POTASSIUM HALIDE AT A TEMPERATURE OF FROM ABOUT 300 TO ABOUT 600*C., THEREBY FORMING A REACTION MIXTURE COMPRISING HYDROGEN CHLORIDE IN ADMIXTURE WITH WATER VAPOR AND CHLORINE IN A REACTION ZONE, THE COMBINATION OF STEPS CONSISTING ESSENTIALLY OF: QUENCHING SAID REACTION MIXTURE IN A QUENCHING ZONE TO A TEMPERATURE IN THE RANGE OF FROM ABOUT 40* TO ABOUT 150*C. WITH HYDROCHLORIC ACID OBTAINED WITHIN THE SYSTEM, SUBJECTING THE RESULTING QUENCHED REACTION MIXTURE TO COUNTERCURRENT DIRECT CONTACT WITH LIQUID SOLVENT FOR HYDROGEN CHLORIDE GAS IN SAID EXTRACTION ZONE, THEREBY SEPARATING A VAPOR OVERHEAD RAFFINATE FRACTION COMPRISING WATER VAPOR AND CHLORINE FROM A LIQUID BOTTOM EXTRACT FRACTION COMPRISING ENRICHED HYDROCHLORIC ACID IN THE BOTTOM OF SAID EXTRACTION ZONE, INTRODUCING LIQUID DILUTE HYDROCHLORIC ACID EMANATING FROM WITHIN THE SYSTEM INTO SAID EXTRACTION ZONE AT AN INTERMEDIATE POINT THEREOF AS SAID SOLVENT FOR HYDROGEN CHLORIDE GAS, INTRODUCING LIQUID WATER AS SUPPLEMENTARY SOLVENT FOR HYDROGEN CHLORIDE GAS INTO SAID EXTRACTION ZONE AT A POINT NEAR THE WITHDRAWAL OF SAID VAPOR OVERHEAD RAFFINATE FRACTION THEREFROM, PASSING A PART OF SAID LIQUID BOTTOM EXTRACT FRACTION FROM SAID EXTRACTION ZONE INTO SAID QUENCHING ZONE TO BE USED THEREIN AS SAID HYDROCHLORIC ACID EMANATING FROM WITHIN THE SYSTEM, PASSING THE REMAINDER OF SAID BOTTOM EXTRACT FRACTION FROM SAID EXTRACTION ZONE INTO A DISTILLATION ZONE, DISTILLING HYDROGEN CHLORIDE FREE OF ANY SUBSTANTIAL AMOUNT OF WATER FROM STILL BOTTOMS CONSISTING ESSENTIALLY OF DILUTE HYDROCHLORIC ACID APPROXIMATING THE HYDROGEN CHLORIDEWATER AZEOTROPE IN SAID DISTILLATION ZONE, PASSING SAID LIQUID STILL BOTTOMS FROM SAID DISTILLATION ZONE INTO SAID EXTRACTION ZONE AT SAID INTERMEDIATE POINT THEREOF TO BE USED THEREIN AS SAID DILUTE HYDROCHLORIC ACID EMANATING FROM WITHIN THE SYSTEM, SEPARATING CHLORINE FROM SAID VAPOR OVERHEAD FRACTION SEAPARATED IN SAID EXTRACTION ZONE, CONTROLLING THE TEMPERATURE AT WHICH SAID DILUTE HYDROCHLORIC ACID AND WATER SOLVENT STREAMS ARE INTRODUCED INTO SAID EXTRACTION ZONE TO MAINTAIN THE TOTAL AMOUNT OF WATER WITHDRAWN OVERHEAD FROM SAID EXTRACTION ZONE AND IN THE UNCONDENSED OVERHEAD ELIMINATED FROM SAID DISTILLATION ZONE SUBSTANTIALLY EQUAL TO THE TOTAL AMOUNT OF WATER INTRODUCED INTO SAID QUENCHING ZONE AND AS SUPPLEMENTARY SOLVENT INTO SAID EXTRACTION ZONE, AND RECYCLING UNCONDENSED OVERHEAD FROM SAID DISTILLATION ZONE TO SAID REACTION ZONE. 